Water-repellent textiles and process of making same



Patented Nov. 7, 1950- WA TER-REPEILENT TEXTILES AND PROCESS OF MAKING John B. Rust, West Orange, N. 1., assignor, by direct and mesne assignments, of one-half to Montclair Research Corporation, a corporation of New Jersey, and one-half to Ellis-Foster Company, a corporation of New Jersey No Drawing. Application November a, 1943,

Serial No. 509,015

- Claims. (01. 117 -1355) This invention relates to water-repellent tex- V tiles and to processes of making the same,

It is known that textile fabrics may be rendered water-repellent by treatment with aqueous solution of certain long chain quaternary ammonium compounds, followed by drying and subsequent baking. Such compounds are typifled by stearoyloxymethyl pyridium chloride and stearamidomethyl pyridium chloride. It has also been disclosed that ceramics and cellulosic materials may be made water-repellent by ex posing them to the vapors of methyl silicon chlorides at room temperature.

The latter process, although being suitable for ceramics, has the great disadvantage of tendering and lowering the tensile strength of textiles due to the hydrochloric acid liberated on-the fibers. No matter how short the period of contact, the acid degrades the textile to some extent, making it useless for some purposes.

Among the objects of the present invention is to provide textile fabrics which are porous and may breathe but which repel and are not wet with water.

Further objects include the production of water-repellent fabrics which are stable to dry cleaning and to laundering.

Still further objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood that this more detailed description is given by way of illustration and explanation only, and not by way of limitation since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with the present invention it has beenfound that textile fabrics may be rendered water-repellent with organO-silicon derivatives and still be made to retain their excellent tensile strength and resistance to wear;

This is accomplished by treating the textile with a substantially neutral-reacting crgano-silicon derivative, desirably applied to the textile by the use of a vehicle carrying such organo-silicon derivative either in solution or dispersion, both water and organic solvents being utilizable for such vehicle. After treatment of the textile as by impregnation with the organs-silicon derivative desirably in a vehicle of the character set forth, the material is fixed on the cloth in any desired way as by means of heat oracid or basic catalysts.

In general, the neutral reacting materials of the present invention may be represented by 2 the'formula R1Si(OR )4-, wherein R is an organic radical selected from the group consisting of aliphatic and carbocyclic groups such as alkyl, aryl, arallwl or cycloaryl, is an integer of fraction of less than 2 but more than zero, and R i hydrogen, or an organic group as set forth immediately above, or an acyl group (R"CO-), and wherein R is hydrogen, or an alkyl, aryl, araikyi or cycloaryl group. These neutral reacting materials may be polymeric hydroxy compounds, alkoxy compounds, or esters. The types of esters that may be employed may be various and are illustrated in application Serial No. 509,016, filed November 3, 1943, and now abandoned, entitled Silicon Derivatives and the Process of Making Same, in the names of Rust and Joy. The organic groups may be alkyl, lmsaturated aliphatics, aryl, aralkyl,

cycloaryl, as illustrated by methyl, ethyl, propyl, butyl, 'amyl, hexyl, phenyl, benzyl, cyclohexyl, and the like. Any desired way of accelerating the cure and fixation of the silicon derivatives to or on the textiles may be utilized but desirably heat is employed for this purpose.

The neutral reacting alkyl silicon derivatives which may be utilized desirably in carrying out the present invention, are preferably selected from the alkyl Silicon-01s, the alkyl alkoxy silicons and the alkyl silicyl esters. In carrying out the processes of the present invention, a proportion of from, say, 1 to 16% of the silicon derivative is applied to the cloth and the derive..- tive fixed thereon by heat or catalytic or other means. More or less of the silicon derivative may be utilized and as indicated above, but in general 5% has been found satisfactory. The amount of silicon derivative which is applied should be sufficient to give the desired waterrepellent property to the fabric while leaving the latter still porous or possessing its property to breathe." Any desired types of textile maerials may be treated including cotton, acetate rayon, viscose rayon, wool, linen and various fabrics produced from synthetic fibers.

In the use of heat for curing and fixing the parts of ethyl ether.

applied or the textile fibers themselves. Usually temperatures of from 120 to 180 C. will be employed depending on the features referred to immediately above. Usually a few minutes treatment at the baking temperatures indicated is suflicient to obtain the desired cure. But in some instances baking for a substantial length of time such as several hours, may be required. The temperature employed and the length of time treatment are mutually interdependent and depend on the nature of the material used for impregnation, the fabric material itself, and the manner of application of the impregnating material.

The following examples are illustrative of the process of the present invention and the products obtainable thereby. All proportions are in parts by weight.

Example 1.A solution of ethyl magnesium bromide in ethyl ether was made from 4.80 parts of magnesium, 21.8 parts of ethyl bromide, and 72 parts of ethyl ether. This solution was added dropwise to 26 parts of ethyl ortho-silicate and 36 parts of ethyl ether and the solution heated for 3 hours at boiling after the addition had been completed. A 27% solution of (C2H5)1.17Si(OCzH5)z.a: was obtained which was diluted to a solution in both acetone and dioxan solvents. A sample of olive drab dyed mercerized poplin was impregnated with solutions and then after drying the cloth was baked at 140 C. for several minutes. A water-repellent cloth was obtained. The above material could also be dissolved in denatured alcohol and applied to poplin. An excellent waterrepellency was obtained after heating for several minutes at 140 C.

Example 2.A solution of ethyl magnesium bromide in ethyl ether was made from 4.80 parts of magnesium, 21.8 parts of ethyl bromide and 72 This solution was added dropwise to 30 parts of silicon tetrachloride in 36 parts of ethyl ether. After all the Grignard solution had been added, the mixture was heated to boiling for 1 hour. When .cool, the precipitated salts were filtered off and washed and 62 parts of n-amyl alcohol added. The ether was distilled off and heating continued at 100 C. until HCl was no longer evolved. 28 parts of the above 18% solution of ethyl amyloxy silicon were dissolved in '72 parts of ethanol and the solution applied to O. D. mercerized poplin. The cloth was dried and baked at 150 C. for several minutes. An excellent water-repellent finish was secured. Standing overnight in a warm humid spot was suflicient to get a repellent efifect on cloth.

The esters employed in the process of the present invention may be described as esters of silicon-ols produced by treating an organic silicon-o1 with an esterifying agent such as an acid anhydride or acid chloride and are desirably organic esters produced with either aliphatic or aromatic carboxylic acids, such as acetic, maleic, betachlorpropionic, benzoic, phthalic, etc., the esters including those of both monobasic and polybasic acids as illustrated above. Examples of producing such esters and their utilization in accordance with the present invention are found below.

Example 3.-A solution of ethyl magnesium bromide formed from 4.86 parts of magnesium, 24 parts of ethyl bromide and 86.4 parts of ethyl ether was added dropwise to 26.1 parts of silicon tetrachloride in 36 parts of ethyl ether. When all the Grignard reagent had been added, the mixture was heated to boiling for 1 hour. The solution was poured onto ice to form the silicols.

washed and dried over anhydrous sodium sulfate.

47 parts of acetic anhydride were added and the ether distilled off. The temperature was taken to C. and kept there for several hours. 10 parts of this acetylated material were dissolved in 165 parts of xylene. This solution was used to impregnate O. D. mercerized poplin. After drying and baking at C. for several minutes a I good water-repellency was secured. A sample of white acetate rayon fabric was treated with the above solution, dried and baked at C. for several minutes. A water-repellent finish was secured.

Example 4.A solution of butyl magnesium bromide formed from 4.86 parts of magnesium, 20 parts of n-butyl bromide and 86.4 parts of ethyl ether, was added dropwise to 22.7 parts of silicon tetrachloride in 36 parts of ethyl ether. After all had been added, the solution was heated to boiling for 1 hour. Then 50 parts of xylene were added and the solution poured onto crushed ice to obtain the polymeric butyl silicols. The ether was distilled off, yielding a 25% solution of the silicols in xylene. This solution was diluted to 5% solids and the solution applied to O. D. poplin. The cloth was dried and baked at 120 C. for several minutes. An excellent water-repellent effeet was obtained which was not removed on three dry cleanings.

Example 5.-A solution of butyl magnesium bromide, formed in the usual manner from 4.86 parts of magnesium, 30 parts of n-outyl bromide and 86.4 parts of ethyl ether, was added dropwise to 28.3 parts of silicon tetrachloride in 36 parts of,

ethyl ether. After the addition was complete, the solution was heated at boiling for 1- hour. -The solution was poured ontocrushed ice, washed, 50 parts of xylene added and dried over sodium sulfate. To 21 parts of the above solution containing 5 parts of (1L-C4H9)1.2Si(OI-I)2.a, 11 parts of stearoyl chloride was added. The mixture was heated to boiling under a reflux condenser for 4 /2 hours. HCl was evolved continuously. 10 parts of the above'solution was diluted with 90 parts of xylene and applied to O. D. poplin after all traces of acid had been removed by washing. The poplin was c'ried and baked at 120 C. for a few minutes. An excellent water-repellency was obtained which was fast to launderings and dry cleanings.

Example 6.*A solution of butyl magnesium bromide, formed in the usual manner from 4.86 parts of magnesium, 30 parts of n-butyl bromide and 86.4 parts of ethyl ether, was added dropwise to 31 parts of silicon tetrachloride in 36 parts of ethyl ether. After the addition was complete, the mixture was heated to boiling for 1 hour, then 50 parts of xylene added. The mixture was poured on crushed ice, washed thoroughly and the ether emoved by distillation. To 15.6 parts of the bove (7lC4H9)1.lSi(OH) 2.9 solution containing 3.3 parts of solids, 4 parts of acetyl chloride were added and the solution'heated to boiling under a reflux condenser for 3 hours. The HCl evolution substantially ceased in this time. A viscous solution resulted indicating polymeric n-butyl silicyl acetate. This was diluted to 5% solids with xylene and applied to poplin. An excellent water-repellency was secured after baking.

Example 7.An ethyl butane siliconate (nC4H9-Si(OC2H5)3) was prepared and 1 mole of this was heated with 1 mole of phthalic anhydride above C. for 5 hours. The phthalic anhydride dissolved completely and a reaction product was formed. The material waswashed rial was used to impregnate O. D. mercerized poplin. The cloth was dried and baked at 130 C. for 2 hours. A good water-repellency was secured, which was fast to dry cleaning.

Example 9.-3 parts of metallic magnesium and 50 parts of butyl ether were placed in a reaction vessel and a trace of methyl iodide was added. A reaction occurred to form some methyl magnesium iodide. 'When this was formed, a mixture of 21.2 parts of silicon tetrachloride and 17.7 parts of methyl iodide was run in and the mixture heated for 3 hours. After pouring onto crushed ice and washing, a solution of methyl silicon trio] was obtained. The solution was thinned to 5% solids with more butyl ether and this solution used to impregnate O. D. poplin. After drying, the poplin was baked at 150 C. for.1 hour. A good water-repellencywas obtained which was fast to laundering.

Example 10.-Methyl silicon trichloride was prepared in ethyl ether by the one-step procedure outlined in Example 9, and cetyl alcohol added in one molar proportion. The mixture was heated to boiling with evolution of HCl. The solution was thinned with benzene and poured into water to form the cetyloxy methyl hydroxysilicon. This solution was used to impregnate a cotton cloth. The cloth was dried and heated to 180 C. for a short time. A highly water-repellent fabric was obtained.

While the production of water-repellent textiles has been particularly emphasized above, other desirable properties including wrinkleproofing and creaseproofing may be secured. Further, dyestuffs are more firmly fixed to the fabric carrying the silicon derivatives of the present invention.

Having thus set forth my invention, I claim:

1. Water-repellent textile comprisin a textile carrying a silicon derivative selected from the group consisting of an alkyl alkoxy silicon and an alkyl silicyl ester fixed thereon by heating at a temperature of 120 to 180 C. in an amount from 1 to to give a light, water-repellent coating without interfering with the breathing property of the textile.

3. Process of making water-repellent textiles which comprises impregnating a textile with a substantially neutral alkyl silicyl ester in amount from 1 to 10% suflicient to give a light waterrepellent coating in the finished textile, which coating does not interfere with the breathing property of the textile, and fixing said ester on the textile by heating at a temperature of 120 to 180 C.

4. Water-repellent textile comprising a textile carrying an alkyl alkoxy silicon fixed thereon by heating at a temperature of 120 to 180 C.

in an amount from 1 to 10% to give a light;

water-repellent coating without interfering with the breathing property of the textile. f

5. Water-repellent textile comprising a textile carrying an alkyl silicyl ester fixed thereon by heating at a temperature of 120 to 180 C. in an amount from 1 to 10% to give a light, waterrepellent coating without interfering with the breathing property of the textile.

6. Water-repellent textile as set forth in claim 4 in which the alkyl alkoxy silicon is ethyl ethoxy silicon.

' 7. Water-repellent textile as set forth in claim 4 in which the alkyl alkoxy silicon is ethyl amyloxy silicon.

8. Water-repellent textile as set forth in calim 4 in which the alkyl alkoxy silicon is n-butyl ethoxy silicon.

9. Water-repellent textile as set forth in claim 5 in which the alkyl silicyl ester is ethyl silicyl acetate.

10. Water-repellent textile as set forth in claim 5 in which the alkyl silicyl ester is n-butyl silicyl acetate.

JOHN B, RUST.

REFERENCES CITED The following references are of record in the file of this patent:

2. Process of making water-repellent textiles 0 which comprises impregnating a textile with a substantially neutral alkyl alkoxy silicon in amount from 1 to 10% sumcient to give a light water-repellent coating in the finished textile, which coating does not interfere with the breathing property of the textile, and fixing said substantially neutral alkyl alkoxy silicon on the textile by heating at a temperature of to C.

UNITED STATES PATENTS Number Name Date 1,809,755 King et a1. June 5, 1931 2,048,799 Lawson July 28, 1936 2,058,844 Vaughn Oct. 27, 1936 2,182,208 Mason Dec. 5, 1939 2,201,840 Venable May 21, 1940 2,253,128 Martin Aug. 19, 1941 2,258,218 Rochow Oct. 7, 1941 2,258,220 Rochow Oct. 7,, 1941 2,258,221 Rochow Oct. 7, 1941 2,258,222 Rochow Oct. 7, 1941 2,306,222 Patnode Dec. 22, 1942 2,386,259- Norton Oct. 9, 1945 2,386,793 Hanford Oct. 16, 1945 FOREIGN PATENTS Number Country Date 113,708 Australia Sept.fi4, 1921 548,911 Great Britain Oct. 29, 1942 Sons 8: Co.. Philadelphia, article alphyl, page 

1. WATER-REPELLENT TEXTILE COMPRISING A TEXTILE CARRYING A SILICON DERIVATIVE SELECTED FROM THE GROUP CONSISTING OF AN ALKYL ALKOXY SILICON AND AN ALKYL SILICYL ESTER FIXED THEREON BY HEATING AT A TEMPERATURE OF 120 TO 180*C. IN AN AMOUNT FROM 1 TO 10% TO GIVE A LIGHT, WATER-REPELLENT COATING WITHOUT INTERFERING WITH THE BREATHING PROPERTY OF THE TEXTILE. 